Electrochemical and Structural Characterization of cis-and trans-[Cp

Organometallics 1998, 17, 1169-1176

1169

Electrochemical and Structural Characterization of cisand trans-[Cp(CO)Ru(µ-As(C6H5)2)]2, Isomers That Undergo Two-Electron-Transfer Oxidations† Anthony-Joseph DiMaio,‡ Arnold L. Rheingold,*,‡ Teen T. Chin,§ David T. Pierce,§,⊥ and William E. Geiger*,§ Departments of Chemistry, University of Delaware, Newark, Delaware 19716, and University of Vermont, Burlington, Vermont 05405 Received November 13, 1997

The structures and oxidations of the cis and trans isomers of the doubly bridged dinuclear species [Cp(CO)Ru(µ-AsPh2)]2 (Ph ) C6H5) have been studied by X-ray crystallography, electrochemistry, and IR and NMR spectroscopies. Each complex oxidizes in a single twoelectron voltammetric process, the E1/2 values being -0.36 V for the cis isomer (1) and -0.30 V for the trans isomer (2) in CH2Cl2/0.1 M [NBu4][PF6] (referenced to ferrocene). These are apparently the first comparative redox potentials published for cis and trans isomers of bridged dinuclear organometallic complexes. Oxidation of 1 to 12+ was cleanly accomplished either by electrolysis or by oxidation of 1 by 2 equiv of ferrocenium, allowing isolation of the dication. The split carbonyl absorptions in the IR spectra of 12+ (νCO ) 2032, 2050 cm-1) are consistent with formation of a Ru-Ru bond in the oxidation reaction. The electrode reaction 1/1+ + e- is much slower than the reaction 1+/12+ + e-, implying that the metalmetal bond is formed in the former process. This conclusion is supported by the observation that the inner-sphere activation barrier, ∆Gq, is about 8.5 kcal/mol, close to that (∼10 kcal/ mol) estimated for a one-electron oxidation involving formation and cleavage of a Ru-Ru bond. The electron-transfer (ET) activation barrier is higher in these Ru complexes than in analogous Fe complexes, which are known to undergo large ET-induced changes in metalmetal bond lengths, most likely because M-M bond strengths are larger when M ) Ru than when M ) Fe. Introduction The electron-transfer (ET) properties of several dinuclear complexes bridged by group 15 or group 16 moieties have been reported.1,2 A number of such complexes can be prepared, or at least generated, having electron counts differing by two, e.g., Fe2(CO)6(µ-S2) and the corresponding dianion.3 The factors affecting both the ET stoichiometries (i.e., one or two ET steps between two-electron products) and energetics are not, however, well understood. The most basic question is whether or not a thermodynamically stable one-electron intermediate (charge ) m + 1 in the drawing) is formed as the molecules transit between the outlying oxidation states, m and (m + 2):

Electrochemistry (cyclic voltammetry, CV, in particular) is a powerful method for probing these ET phenom† Structural Consequences of Electron-Transfer Reactions. 34. For part 33, see: Geiger, W. E.; Shaw, M. J.; Wu¨nsch, M.; Barnes, C. E.; Foersterling, F. H. J. Am. Chem. Soc. 1997, 119, 2804. ‡ University of Delaware. § University of Vermont. ⊥ Present address: Department of Chemistry, University of North Dakota, Grand Forks, ND 58202.

ena. Examples are known in which the overall twoelectron process has the voltammetric characteristics of a single Nernstian two-electron wave, with E1/22 , E1/21,4 a pair of unresolved one-electron waves (E1/22 ≈ E1/21),5 two well-separated one-electron waves (E1/22 . E1/21),6,7 or an ECE process.8 Although one expects that structural changes in the ET series, specifically changes in M-M bond length and M-bridging atom-M bond angles, will influence the values of ∆E1/2(dE1/22-E1/21) and the charge-transfer rates of the couples,6,7,9,10 the relationships among these factors are still unclear.5,7 (1) Geiger, W. E.; Connelly, N. G. Advances in Organometallic Chemistry; Stone, F. G. A., West, R., Eds.; Academic Press, Inc.: Orlando, FL, 1985; Vol. 24, pp 98-110. (2) Astruc, D. Electron-Transfer and Radical Processes in Transition Metal Chemistry; VCH Publishers: New York, 1995; pp 247 ff. (3) (a) Seyferth, D.; Henderson, R. S.; Song, L. J. Organomet. Chem. 1980, 192, C1; (b) Organometallics 1982, 1, 125. (4) [(CO)3Fe(µ-PPh2]20/2-: Collman, J. P.; Rothrock, R. K.; Finke, R. G.; Moore, E. J.; Rose-Munch, F. Inorg. Chem. 1982, 21, 146. (5) [(CO)4W(µ-SBz)]22-/0 (Bz ) benzyl): (a) Fernandes, J. B.; Zhang, L. Q.; Schultz, F. A. J. Electroanal. Chem. 1991, 297, 145. (b) Hill, M. G.; Rosenhein, L. D.; Mann, X. R.; Mu, X. H.; Schultz, F. A. Inorg. Chem. 1992, 31, 4108. (6) (CO)6Mn2(µ-SR)3-/0/+ (a) McDonald, J. W. Inorg. Chem. 1985, 24, 1734. (b) Lyons, L. J.; Tegan, M. H.; Haller, K. J.; Evans, D. H.; Treichel, P. M. Organometallics 1988, 7, 357. (7) [Cp(CO)Fe(µ-PPh2)]2, [Cp(CO)Fe(µ-SMe)]2, and [CpMo(µ-SMe)2]2: Gennett, T.; Geiger, W. E.; Willett, B.; Anson, F. C. J. Electroanal. Chem. 1987, 222, 151. (8) Cp*2Fe2S40/2+: Inomata, S.; Tobita, H.; Ogino, H. Inorg. Chem. 1991, 30, 3039. (9) Marcus, R. A. Annu. Rev. Phys. Chem. 1964, 15, 155.

S0276-7333(97)00999-0 CCC: $15.00 © 1998 American Chemical Society Publication on Web 02/26/1998

1170 Organometallics, Vol. 17, No. 6, 1998

In an attempt to learn more about this problem, we have investigated the oxidation of cis-[Cp(CO)Ru(µAsPh2)]2 (1) and (less extensively) its trans isomer, 2.

In contrast to their first-row analogue [Cp(CO)Fe(µPPh2)]2, which undergoes two well-separated (∆E1/2 ≈ 350 mV) one-electron oxidations,7 the two diruthenium complexes show single two-electron anodic waves that deviate from Nernstian behavior only at higher CV sweep rates. Although the dication 12+ proved isolable, X-ray quality crystals of it were not obtained. The crystal structures of the two neutral complexes were obtained, however, providing a rare comparison of the molecular structure of cis- and trans-isomers of a bridged dinuclear system. The dication was characterized by spectroscopic methods, and the couple 1/12+ was shown to constitute a chemically reversible two-electron redox system, with the neutral-to-monocation ET being the rate-determining step. Experimental Section Materials. [CpRu(CO)2]211 and cyclo-(C6H5As)612 were prepared according to literature procedures. Hydrocarbon solvents were distilled under nitrogen from sodium/benzophenone, while halogenated solvents were dried over molecular sieves. Thermolysis of [CpRu(CO)2]2 with cyclo-(C6H5As)6. A solution in a 40-mL heavy-wall Carius tube containing 0.308 g of [CpRu(CO)2]2 (0.695 mmol), 0.640 g of cyclo-(C6H5As)6 (0.701 mmol), and 15 mL of toluene was degassed using three freeze-pump-thaw cycles and then flame sealed. The tube was placed inside an end-capped steel pipe with several small vents. (Caution: Pressures within the tube may reach 10-20 atm at the maximum temperature. Ruptures occur in about 10% of the tubes prepared in this manner. Tubes can be most safely opened after cooling the contents in liquid nitrogen.) The tube was heated in an oven at 180 °C for 65 h and then slowly cooled to room temperature. The tube was opened, and its contents were filtered and washed with toluene. The solvent was removed from the filtrate to give a reddish tar. The tar was redissolved in a minimum volume of CH2Cl2 and then chromatographed on an alumina column. After an initial flush of the column with hexanes to remove excess cyclo(C6H5As)6, a gradient mixture of CH2Cl2 in hexanes was used to elute the column. The first major product fraction appeared as a yellow band with 20% CH2Cl2. 1H NMR spectra showed the presence of two cyclopentadienyl compounds in this and subsequent bands that varied quanititatively, indicating the presence of two products. All fractions containing these two proton resonances were combined, and a second alumina column, eluted with 15% CH2Cl2 in hexanes, separated the mixture into two products, both yellow-orange. Both samples were recrystallized from acetone/hexanes. X-ray diffraction identified these compounds as the cis (1, 30% yield) and trans (2, 10%) isomers of [Cp(CO)Ru(µ-AsPh2)]2. For 1: IR (CHCl3) (10) Geiger, W. E. In Progress in Inorganic Chemistry; Lippard, S. J., Ed.; John Wiley: New York, 1985; Vol. 33, p 275. (11) (a) Humphries, A. P.; Knox, S. A. R. J. Chem. Soc., Dalton Trans. 1975, 1710. (b) Blackmore, T.; Bruce, M. L.; Stone, F. G. A. J. Chem. Soc. A 1968, 2158. (12) Palmer, C. S.; Scott, A. B. J. Am. Chem. Soc. 1928, 50, 536.

DiMaio et al. νCO ) 1958(s), 1925(m); UV/vis (CHCl3, 4.4 × 10-5 M) bands observed at 205 ( ) 9773), 245 (26 704), and 330 nm (6477) (the 330-nm band tails off at 470 nm); 1H NMR (CDCl3) δ ) 7.62 (dd, l0H), 7.35 (m, 10H), 4.59 (s, 10H); 13C NMR (CDCl3) δ ) 207 (s), 145 (s), 138 (s), 134 (s), 131 (s), 127 (q), 82 (s); MS parent ion at m/z ) 847 (isotope pattern for two Ru atoms). Elemental analysis: C, 50.67; H, 3.44; As, 16.9 (calcd C, 51.07, H, 3.57, As, 17.70) (Galbraith). For 2: IR (CHCl3) νCO ) 1957(s); UV/vis (CHCl3, 2.48 × 10-5 M) bands at 240 ( ) 23 790) and 337 nm (6250) (the 337-nm band tails off at 450 nm); 1H NMR (CDCl3) δ ) 7.63 (dd, 10H), 7.32 (s, 16H), 4.52 (s, 10H); 13C NMR (CDCl3) δ ) 141 (s), 139 (s), 134 (s), 133 (s), 129 (d), 127 (d), 83 (s). Elemental analysis: C, 50.85; H, 3.72; As, 16.8 (Galbraith). [cis-{Cp(CO)Ru(µ-AsPh2)}2][PF6]2. A CH2Cl2 solution containing 30 mg (35 µmol) of 1 and 23 mg (70 µmol) of ferrocenium hexafluorophosphate13 was stirred at room temperature for 1 h. During this time, the color of the solution changed from the green of 1 to yellow-green, and a precipitate was deposited. After filtration, the solid was washed copiously with diethyl ether to remove ferrocene. Recrystallization from CH3NO2/ethyl ether at 243 K gave small yellow crystals of the desired dication (19 mg, 41%) (elemental analysis by Robertson Laboratories: C, calcd 38.02, found 36.80; H, calcd 2.64, found 2.52): 1H NMR (CD3NO2) δ ) 6.03 (s, Cp), 7.30-7.55 (m, Ph); IR (CH2Cl2) νCO ) 2050, 2032 cm-1; IR Nujol) νCO ) 2043, 2023 cm-1; PF6- at 850 cm-1. Electrochemistry. Measurements were conducted under an atmosphere of dinitrogen within a drybox, using solvents and procedures previously described.14 The working electrodes were commercially available disks, except in the case of rotating platinum electrode scans, for which a homemade Pt bead mounted through soft glass was employed. A synchronous rotator (Sargent, 1800 rpm) was used in rotating electrode experiments. The disk diameters were nominally 1 mm, except for the larger (Beckman) electrode used for chronoamperometry experiments. The electrochemical area of the larger electrode was calibrated as 0.393 cm2 using the oxidation of K4[Fe(CN)6] in aqueous 2 M KCl.15 Disk electrodes were polished with a series of diamond pastes, finishing with a particle size of 0.25 µm. Potentials in the paper are quoted vs the ferroceneferrocenium couple, as recommended by IUPAC.16 Ferrocene was added to the analyte solutions as an internal standard at an appropriate point in the experiment. Conversion to the aqueous SCE scale may be achieved by addition of 0.46 V for CH2Cl2 solutions and 0.40 V for DMF solutions. In all cases, the supporting electrolyte was 0.1 M [NBu4][PF6]. Digital simulations of CV scans were performed originally with a program for EE mechanisms written at the University of Vermont, based on the explicit finite difference method of Feldberg,17 but later confined using DIGISIM (Bioanalytical Systems). X-ray Structural Characterization. Crystallographic data for 1 and 2 are collected in Table 1. Both were found to possess 2/m Laue symmetry. For 1, systematic absences in the diffraction data and the presence of two-fold rotational symmetry along an axis aligned with the crystallographic b axis indicated that the correct space group was C2/c. For 2, systematic absences uniquely indentified the space group as P21/c. Empirical corrections for absorption was made using ψ-scan data. Both structures were solved by direct methods and refined with anisotropic parameters for all non-hydrogen (13) Connelly, N. G.; Geiger, W. E. Chem. Rev. 1996, 96, 877. (14) Chin, T. T.; Geiger, W. E.; Rheingold, A. L. J. Am. Chem. Soc. 1996, 118, 5002. (15) Adams, R. Electrochemistry at Solid Electrodes; Marcel Dekker: New York, 1969; p 124. (16) Gritzner, G.; Kuta, J. Pure Appl. Chem. 1984, 56, 461. (17) Feldberg, S. W. In Electroanalytical Chemistry; Bard, A. J., Ed.; Marcel Dekker: New York, 1969; Vol. 3, p 199.

cis- and trans-[Cp(CO)Ru(µ-As(C6H5)2)]2

Organometallics, Vol. 17, No. 6, 1998 1171

Table 1. Crystallographic Data for cis- and trans-[CpRu(CO)As(C6H5)2]2 cis formula crystal system space group a, Å b, Å c, Å b, deg V, Å3, Z cryst dimens, mm crystal color D(calc), g cm3 m(Mo KR), cm-1 temp, K diffractometer 2θ scan range, deg no. rflns colltd, indpt, obsvd R(F), R(wF) %a ∆(F), e Å-3 GOF

trans

(a) Crystal Parameters C36H30O2As2Ru2 C36H30O2As2Ru2 monoclinic monoclinic C2/c P21/c 9.443(3) 21.860(1) 36.037(12) 15.544(3) 9.663(2) 18.92(1) 98.34(2) 96.98(4) 3253(2), 4 6380(5), 8 0.15 × 0.30 × 0.35 0.24 × 0.25 × 0.42 orange orange 1.73 1.76 49.74 50.72 296 296 (b) Data Collection Nicolet R3 Nicolet R3 4 g 2θ g 50 4 g 2θ g 50 3108, 2878, 2057 12 075, 11 242, 6771 (c) Refinement 3.40, 4.53 0.481 1.04

4.40, 5.16 1.015 1.05

Figure 1. Molecular structure of cis-[CpRu(CO)(µ-AsPh2)]2 (1), with atoms represented as 40% thermal ellipsoids.

a Quantity minimized ) ∑∆2; R ) ∑∆/∑(F ); R(w) ) ∑∆w1/2/ o ∑(Fow1/2), ∆ ) |(Fo - Fc)|.

atoms. Hydrogen atoms were treated as idealized contributions. All computations used SHELXTL (ver. 4.2, G. Sheldrick, Siemens XRD, Madison, WI).

Results and Discussion Synthesis and Structures. The reaction of [CpRu(CO)2]2 with the homocycle cyclo-(AsC6H5)6 in a sealed tube at 145 °C in toluene leads to a disproportionation of the phenylarsenido group to form diphenylarsenidobridged and naked arsenic clusters. No naked arsenic clusters were isolable, but, from solution spectroscopic data and analogy to earlier work with cyclopentadienyl Fe18 and Mo19 carbonyl reactions under similar conditions, it is likely that these are tetrahedrane analogues of general formula [CpRu(CO)]mAsn. The bridged diphenylarsenido complexes formed have been crystallographically characterized as the cis (1) and trans (2) isomers of [CpRu(CO)(µ-AsPh2)]2 (Figures 1 and 2). 1 and 2 are separable by column chromatography and are produced in a 3:1 ratio:

[CpRu(CO)2]2 + cyclo-(AsC6H5)6 f [CpRu(CO)µ-As(C6H5)2]2 + [CpRu(CO)]mAsn cis (1) and trans (2) The cis isomer 1 crystallizes in the monoclinic space group C2/c; selected bond parameters are given in Table 2. There is a crystallographically imposed two-fold rotation axis located at the centroid of the Ru2As2 rhombus, which it generates and to which it is perpendicular. The average ruthenium-arsenic bond is 2.455 Å. The Ru2As2 framework is virtually planar; the angle formed by the two RuAs2 planes in the rhombus is 179.3(1)°. Ruthenium exhibits a distorted octahedral environment if the Cp ring is viewed as occupying three (18) Sinclair, J. D. Ph.D. Dissertation, University of Wisconsin, Madison, WI, 1972. (19) Sullivan, P. J.; Rheingold, A. L. Organometallics 1982, 1, 1547.

Figure 2. Molecular structure of trans-[CpRu(CO)(µAsPh2)]2 (2), with atoms represented as 40% thermal ellipsoids. One of two independent molecules is shown.

coordination sites. The most acute angle found is at As-Ru-As(a), 75.2(1)°. A slightly distorted tetrahedral environment is seen at arsenic; the smallest angle found about arsenic is that between the two phenyl rings, C(16)-As-C(26) ) 99.9(1)°. The phenyl rings about arsenic are situated such that those on the same side of the Ru2As2 plane as the Cp rings are rotated to fit the space available. The rings are contained in an approximate plane formed by the As and ipso C atoms. The other two phenyl rings are twisted so that they are essentially perpendicular to this plane. For the trans isomer 2, two independent molecules crystallize in the monoclinic space group P21/c; selected bond parameters are given in Table 2. There are only minor deviations in the bond lengths and angles for the


DiMaio et al.

Table 2. Selected Bond Distances and Angles for cis- (1) and trans-[CpRu(CO)µ-As(C6H5)2]2 (2) 2

1

Ru-As Ru-As(a)

2.457(1) 2.453(1)

Ru-CNT

1.897(8)

Ru‚‚‚Ru(a)

3.884(1)

As-Ru-As(a) As-Ru-C(1) AS(a)-Ru-C(1) As-Ru-CNT As(a)-Ru-CNT CNT-Ru-C(1)

75.2(1) 88.5(2) 89.6(2) 130.7(2) 127.3(2) 128.6(2)

Ru-As-Ru(a) C(16)-As-C(26)

104.5(1) 99.9(1)

molecule A

molecule B

(a) Bond Distances (Å) Ru(1)-As(1) Ru(1)-As(2) Ru(2)-As(1) Ru(2)-As(2) Ru(1)-CNT1 Ru(2)-CNT2 Ru(1)‚‚‚Ru(2)

2.485(1) 2.478(1) 2.461(1) 2.459(1) 1.886(6) 1.900(7) 3.872(1)

2.466(1) 2.469(1) 2.457(1) 2.463(1) 1.894(7) 1.891(7) 3.843(1)

(b) Bond Angles (deg) As(1)-Ru(1)-As(2) As(1)-Ru(1)-C(6) As(2)-Ru(1)-C(6) As(1)-Ru(1)-CNT1 As(2)-Ru(1)-CNT1 CNT1-Ru(1)-C(6) As(1)-Ru(2)-As(2) As(1)-Ru(2)-C(12) As(2)-Ru(2)-C(12) As(1)-Ru(2)-CNT2 As(2)-Ru(2)-CNT2 CNT2-Ru(2)-C(12) Ru(1)-As(1)-Ru(2) C(26)-As(1)-C(36) Ru(1)-As(2)-Ru(2) C(46)-As(2)-C(56)

75.8(1) 96.9(3) 93.7(2) 125.2(3) 128.2(2) 124.1(2) 76.5(1) 88.8(2) 86.3(2) 130.3(2) 128.8(3) 128.8(3) 103.1(1) 96.4(2) 103.3(1) 97.3(2)

74.3(1) 91.9(3) 100.6(3) 129.6(2) 122.2(3) 124.9(2) 74.6(1) 85.1(3) 89.7(3) 132.7(2) 129.8(3) 127.4(3) 102.6(1) 101.1(2) 102.3(2) 97.8(3)

two molecules. The average Ru-As bond is 2.467 Å, which is slightly longer than that found in 1. Again, the Ru2As2 rhomboid is flat; the angle formed by the two RuAs2 planes is 179.3(1)°. The local Ru atom geometry is again distorted octahedral, with the largest angles found about the Cp centroid-ruthenium vector, and the smallest angles found within the As-Ru-As portion of the rhombus. Arsenic again exhibits distorted tetrahedral geometry, with the phenyl-As-phenyl angle consistently being acute. The phenyl rings about arsenic in 2 are oriented in a slightly different manner from those of 1. Each pair of phenyl rings lies tilted slightly in deference to the Cp ring located on that side of the Ru2As2 plane. The Ru‚‚‚Ru distances in both 1 (3.884(1) Å) and 2 (av 3.858 Å) preclude direct metalmetal interactions. The structures of 1 and 2 are the first published for iron triad metals in bridged dinuclear complexes of the type [CpM(CO)(µ-ER2)]2 and only the second for a related complex of any dinuclear cyclopentadienyl metal complex with bridging diorganoarsenido groups, the first being [CpMo(CO)2(µ-AsMe2)]2.20 Additionally, isomers 1 and 2 constitute only the second example of an isolated and crystallographically characterized set of cis-trans isomers for any bis-diorganopnictido-bridged structure of the very general formula [CpMn(ER2)]2, the first being [CpCr(NO)N(CH3)2]2.21 Conversion of 1 to 2, or vice versa, by thermal means was not possible. Even after 72 h at 160 °C, there was no evidence for conversion of a toluene solution as monitored by 1H NMR. However, it is possible to convert the cis isomer 1 to the trans isomer 2 irreversibly and in 90% yield after a 4-h exposure at room temperature with a low-pressure photochemical apparatus emitting at about 360-440 nm. The photochemical conversion of cis to trans may proceed via RuAs bond breaking and inversion at Ru. The Mo-As (20) Gross, E.; Burschka, C.; Malisch, W. Chem. Ber. 1986, 119, 378. (21) Bush, M. A.; Sim, G. A. J. Chem. Soc. A 1970, 611.

bond breaking/Mo inversion scenario was proposed for the cis f trans photochemical process in [CpMo(CO)2(µ-AsMe2)]2.22 These results imply that 1 is the kinetic product, while 2 is the thermodynamically favored product. Electrochemical Oxidation of 1: Two-Electron Stoichiometry. Complex 1 displays a single anodic wave (Figure 3) in CH2Cl2 or DMF with E1/2 values (computed from average of Epa and Epc) of -0.36 and -0.30 V, respectively (Table 3). The oxidation was established as a chemically reversible two-electron process (eq 1) by cyclic voltammetry (CV), double-

1 h 12+ + 2e-

(1)

potential step chronoamperometry (CA), and bulk coulometry experiments. CV scans in CH2Cl2 at ambient temperatures gave a ratio of ic/ia of slightly above unity with scan rates as low as 0.05 V/s. CA gave a reverse-to-forward current ratio, irev/ifwd, at the end of a 5-s step time, of 0.29, in agreement with expectations for formation of a stable electrode product.23 The CV current function (ipa/ν1/2)24 was exactly twice that of equimolar decamethylferrocene.25 CV peak separations, ∆Ep ()Epa - Epc), were about 40 mV, and the anodic peak breadth, δEp ()Ep Ep/2), was 34 mV, with ν ) 0.05 V/s. The two-electron nature of the process was finally confirmed by bulk coulometry, in which 2.1 F/equiv was released when 1 was electrolyzed to 99% completion at a Pt basket, with Eappl ) 0 V at T ) 273 K. (22) Malisch, W.; Kuhn, M.; Albert, W.; Ro¨ssner, H. Chem. Ber. 1980, 113, 3318. (23) Theory for a completely reversible couple, 0.293 (Schwarz, W. M.; Shain, I. J. Phys. Chem. 1965, 69, 30); experiment for ferrocene under our conditions, 0.284. (24) Geiger, W. E. In Laboratory Techniques in Electroanalytical Chemistry, 2nd ed.; Kissinger, P. T., Heineman, W. R., Eds.; Marcel Dekker: New York, 1996; p 683. (25) This demonstrates that the oxidation of 1 is a two-electron process if the diffusion coefficients of 1 and decamethylferrocene are similar.



reversible two-electron process of eq 1 [E1/2 ) -0.30 V; ic/ia ) 1.05 at ν ) 0.05 V/s; irev/ifwd ) 0.29 for 5-s CA step time; Do ) 2.5 × 10-6 cm2/s (from CA)]. The isolated dication (see below) also had E1/2 ) -0.30 V in DMF. In every published example of which we are aware, a two-electron wave for a bridged dinuclear complex has been ascribed to the making and breaking of a metalmetal bond accompanying the overall charge transfer(s).30 The voltammetry is, therefore, interpreted in light of such a model; as the next section shows, the structural changes are likely apportioned between the two one-electron steps, with the major change occuring in the first electron transfer:

Figure 3. Cyclic voltammetry scans of 0.5 mM 1 in DMF/ 0.1 M [NBu4][PF6] at 295 K: top, ν ) 0.05 V/s; bottom, ν ) 1 V/s. Table 3. Electrochemical Potentials of 1 and 2 (Volts vs Fc) complex 1 1 12+ 1 2

product 12+ 12+ 1 12- b 22+

solvent

E1/2

D0 (cm2/s)

CH2Cl2 DMF DMF DMF CH2Cl2

-0.36 -0.30 -0.30 -2.3b -0.30

a 2.5 × 10-6 a a 8.7 × 10-6

Deviations from Reversible Voltammetry: Use of Higher Scan Rates To Estimate ElectronTransfer Rate Constants for 1. The CV responses of 1 at higher scan rates are of interest because, under quasi-reversible charge-transfer conditions, some information may be extracted about the individual oneelectron processes that make up the overall two-electron transfer.14,27,30 ∆Ep values increased with increases in ν for either CH2Cl2 or DMF solutions of 1. Anodic peak potentials (Epa) also increased, and anodic current functions (χa ) ipa/ν1/2) decreased at higher scan rates. No new peaks or other features were detected up to ν ) 100 V/s, nor were the voltammetric wave shapes affected by changes in concentration of 1 from 0.28 to 1.10 mM. The two functions Epa, and χa, though less widely employed as diagnostics than ∆Ep values, shed light on the ET reversibility of the electrode reaction. Figure 4 shows their values as the oxidation process goes from nearly Nernstian behavior (low ν) to one which displays irreversible charge-transfer kinetics (high ν). The current function is expected to decrease according to eq 2,

a Not measured. b Irreversible reduction wave of two-electron height; Epc at ν ) 0.1 V/s given.

χa(irrev) ) 1.11(RnR)1/2χa(rev)

Solutions of 12+ generated coulometrically were stable in CH2Cl2, and the back-reduction of 12+ to 1 at Eappl ) -0.6 V was efficient (2.1 F/equiv also found in the cathodic electrolysis of 12+). Only about 10% lower current was found in RPE voltammograms of 1 after the bulk oxidation/reduction cycle. Every indication, therefore, points to the adequacy of eq 1 as a description of this redox process. It is worth noting that the diffusion coefficient (D0) of 12+ is, apparently, substantially lower than that of 1. This conclusion is indicated by the fact that a current plateau of 3.7 µA was measured for 1 prior to bulk electrolysis, but only 2.7 µA was observed for 12+ after the anodic reaction. Considerably reduced diffusion coefficients have been found previously for dications in CH2Cl2 compared to their neutral precursors.14,26-29 Complex 1 was also studied in DMF, a solvent superior to CH2Cl2 for quantitative fast voltammetry. Its oxidation was again described by the chemically

in which R is the charge-transfer coefficient, nR is the number of electrons transfered in the rate-determining step, and χ(irrev) and χ(rev) are the current functions for electrode reactions in the irreversible and Nernstian limits, respectively. The limiting current function for 1 at high sweep rates is consistent with R ) 0.4 and nR ) 1. The shifts in anodic peak potentials at high ν also are consistent with R ) 0.4, nR ) 1, as shown by the straight line in Figure 4 computed from eq 3:

(26) Edwin, J.; Geiger, W. E. J. Am. Chem. Soc. 1990, 112, 7104. (27) Pierce, D. T.; Geiger, W. E. J. Am. Chem. Soc. 1992, 114, 6063.

d(Ep)/d(log ν) ) 30 mV/RnR

(2)

(3)

(28) In well-defined hydrodynamic circumstances (e.g., a rotating disk electrode), the relative values of the diffusion coefficients for the reduced and oxidized forms of the redox couple may be obtained from the plateau currents prior to and subsequent to, respectively, an anodic electrolysis. Quantitative comparisons are less certain when the (empirically shaped) Pt bead electrode is used.29 A reasonable estimate is that the diffusion coefficient of 12+ is about one-half of that of 1 in CH2Cl2. (29) Sawyer, D. T.; Roberts, J. L., Jr. Experimental Electrochemistry for Chemists; John Wiley and Sons: New York, 1974; p 91. (30) For leading citations, see refs 5, 6, 10, and 14.


DiMaio et al.

Figure 4. Anodic current function (9, left ordinate) and anodic peak potential (b, right ordinate) as a function of CV scan rate for 1 in DMF at 295 K. The current function is ratioed to the value at low sweep rates (the Nernstian limit). Line a gives the expected slope in the irreversible limit for a process with R ) 0.4, and line b gives the expected current function in the irreversible limit for R ) 0.4.

The data in Figure 4 tell us that the quasi-reversible charge-transfer regime lies at scan rates below 10 V/s for the oxidation of 1, so we now turn to this scan rate region to estimate the quantitative electron transfer parameters of 1. Figure 5 shows a CV recorded at ν ) 1 V/s. The fact that the anodic peak height is less than the cathodic peak height means that the first charge-transfer step is rate limiting,31 consistent with the dominant structural change occurring in the process 1/1+. In digital simulations, we set the value of (E1/22 - E1/21) at -180 mV, based on the nearly Nernstian behavior of the couple32 at slow sweep rates and the value of ks(2) at 0.1 cm/s, consistent with findings for related systems.5a,7 In fact, the simulations have little sensitivity to the precise value of ks(2), since the value of ks(l) is rate limiting. Simulations such as those shown in Figure 5 were consistent with the values ks(l) ) 0.007 ( 0.002 cm/s and R(1) ) 0.42 ( 0.05. As a test of internal consistency, the R value agrees with that implied from the changes in current function and anodic peak potential with scan rate (Figure 4, vide ante). Preparation of 12+ by Chemical Oxidation. Oxidation of 1 using 2 equiv of ferrocenium hexafluorophosphate in CH2Cl2 gave a yellow-green solid which, when recrystallized from CH3NO2/diethyl ether, produced fine needles which analyzed as [1][PF6]2. When this reaction was carried out in an NMR tube in CD2Cl2, the Cp 1H resonances of 1 (δ ) 4.63) and 12+ (δ ) 6.03) were observed, without evidence of intermediates or side products. IR spectra of 12+ in CH2Cl2 gave a pair of CO stretches at 2050 and 2032 cm-1, shifted an average of +87 cm-1, from the single νCO of 1 at 1954 cm-1. The split band in the dication is significant, since the implied vibronic coupling between the CO groups is consistent with the presence of a metal-metal bond in 12+. The dication [1][PF6]2 displayed the expected voltammetry in DMF, i.e., a single reduction wave at E1/2 ) -0.30 V (cf. Figure 6). (31) Ryan, M. D. J. Electrochem. Soc. 1978, 125, 547. See also citations contained in ref 27. (32) Polcyn, D. S.; Shain, I. Anal. Chem. 1966, 38, 370.

Figure 5. Fits between theory (solid lines) and experiment (dots) for the oxidation of 1.0 mM 1 in DMF at 298 K and (top) 10 V/s and (bottom) 1 V/s. Simulation parameters: E1/21 ) -0.27 V, R1 ) 0.42, kS(1) ) 0.007 cm/s; E1/22 ) -0.45 V, R2 ) 0.50, kS(2) ) 0.1 cm/s.

Electrochemical Properties of 2. The trans isomer 2 also undergoes a two-electron oxidation in CH2Cl2 to a persistent dication.33 Its potential (E1/2 ) -0.30 V) was 60 mV positive of that of the cis isomer 1 in the same medium. The dication 22+ did not appear to be as stable as 12+: about one-third of 2 was lost in a bulk coulometry experiment in which 22+ was generated at 273 K and then re-reduced back to neutral 2. Significance of Electron-Transfer Properties. The difference in E1/2 values for the two isomers, although small (60 mV), shows that cis and trans isomers of dinuclear systems may have resolvable formal potentials. There is no evidence for interconversion of the two isomers in either of the higher oxidation states. Although worth noting, this observation may not be general for dinuclear bridged complexes, since the formation of a metal-metal bond in the dication may impart isomeric rigidity to the complexes that might be otherwise lacking. Of, perhaps, greater interest is the contrast between the present diruthenium complexes and their diiron analogues having sulfido or phosphido bridges. Both [Cp(CO)Fe(µ-PPh2]2 (3) and [Cp(CO)Fe(µ-SMe)]2 (4) may (33) In CV at ν ) 0.05 V/s, ic/ia ) 1.08, ∆Ep ) 34 mV, Ep - Ep/2 ) 28 mV; double-potential step chronoamperometry, irev/ifwd ) 0.27 (5-s pulses); bulk coulometry, 1.9 F/equiv for 99% electrolysis (all data at Pt electrodes).



rier is one-fourth of the inner-sphere reorganizational energy, λin (eq 5).

∆GqIS ) λin/4

(5)

In the limit that there is localized bond making and breaking in the ET transition state, the inner-sphere reorganizational energy is essentially equal to the bond enthalpy.34 The latter may be estimated for a Ru-Ru bond of ≈2.8 Å from the work of Connor35 as ≈20 kcal/ mol. This suggests a value of ∆GqIS ≈ 5 kcal/mol if the Ru-Ru bond is fully formed in the first one-electron transfer 1/1+. Using an estimate of 5 kcal/mol for ∆GqOS,36 an overall value of ≈10 kcal/mol is predicted for a one-electron process involving full formation of a Ru-Ru single bond in the transition state. Given the uncertainties involved in these estimates, the observed value of 8.5 kcal/mol is respectably close to the prediction of this model.37

Figure 6. Cyclic voltammetric scans for 1 (top) and 12+ (bottom) in identical media (CH2Cl2/0.1 M [NBu4][PF6]) prior to (top) and after (bottom) exhaustive electrolysis (Eappl ) 0 V) of a 1 mM solution of 1. Scan rate, 0.2 V/s; T ) 273 K.

be oxidized to dications, but their oxidations differ from those of 1 and 2 in (i) being well-separated one-electron processes and (ii) exhibiting fast electrode kinetics.7

Factor i argues that the energy of the one-electron (monocation) intermediate is lowered more in the Ru2 case than in the Fe2 case, compared to the two outlying oxidation states. Factor ii, when contrasted with the slow:fast character of the two one-electron transfers 1/1+:1+/12+, argues that the major part of the structural change in the diruthenium system comes in the first of these ET steps, in contrast to a more distributed set of structural changes in the diiron systems. Stated in another way, the M-M bond formation is more gradual in the sequence Fe2/Fe2+/Fe22+ than in the sequence Ru2/ Ru2+/Ru22+, where M2 stands for the dinuclear complexes under discussion. The activation barrier to ET, ∆Gq, consists of innersphere and outer-sphere contributions, ∆GqIS and ∆GqOS, respectively (eq 4). Furthermore, the inner-sphere bar-

∆Gq ) ∆GqIS + ∆GqOS

(4)

Conclusions The cis and trans isomers of [Cp(CO)Ru(µ-AsPh2)]2 have been prepared and characterized by X-ray crystallographic methods. Both isomers display single anodic voltammetric waves of two-electron stoichiometry, the cis isomer being 60 mV easier to oxidize than the trans isomer. There is little previous literature on the question of whether cis and trans isomers of bridged dinuclear complexes have measureably different redox potentials.38 The dication of the cis isomer, 12+, has been isolated and characterized by NMR and IR spectroscopies. The presence of two CO stretches in the IR spectrum of 12+ is evidence that the dication possesses the expected RuRu bond. The CV waves are essentially Nernstian at slow sweep rates but become quasi-reversible at higher scan rates. The wave shapes of the cis isomer are fit quantitatively by E1/21, ) -0.27 V vs Fc, E1/22 ) -0.45 V, R1 ) 0.42, R2 ) 0.5, kS(1) ) 0.007 cm/s, and kS(2) > 0.1 cm/s. The fact that the first oxidation is the rate-determining anodic process suggests that a major structural change occurs in electron transfer between the neutral and monocationic complexes. An activation barrier, ∆Gq, of 8.5 kcal/mol is consistent with the metal-metal bond being formed largely in this step. The differences in electrode behavior between the present diruthenium complexes and their diiron analogues are explicable in terms of the presence of a stronger M-M bond in the one-electron intermediate formed upon oxidation of the diruthenium complexes. (34) (a) Saveant, J. M. In Advances in Electron Transfer Chemistry; Mariano, P. S., Ed.; JAI Press: New York, 1994; Vol. 4, p 53. (b) Andrieux, C. P.; Robert, M.; Saveant, J. M. J. Am. Chem. Soc. 1995, 117, 9340 and references therein. (35) Connor, J. A. In Transition Metal Clusters; Johnson, B. F. G., Ed.; John Wiley and Sons: Chichester, 1980; p 356. (36) Weaver, M. J.; Gennett, T. Chem. Phys. Lett. 1985, 113, 213. (37) From a value of 0.007 cm/s for ks(1) and an assumed preexponential term of 104, ∆Gq ) 0.38 eV (8.5 kcal/mol) at room temperature. For an introductory treatment of these concepts, see: Hale, J. M. In Reactions of Molecules at Electrodes; Hush, N. S. Ed.; Wiley-Interscience: London, 1971; p 229. (38) The inorganic dinuclear complex [(triphos)(H)Rh(µ-Cl)]2 has been reported to display a single irreversible reduction wave for a 1:1 solution of trans:cis isomers: Bianchini, C.; Meli, A.; Laschi, F.; Ramirez, J. A.; Zanello, P.; Vacca, A. Inorg. Chem. 1988, 27, 4429.


Acknowledgment. This work was supported in part by the donors of the Petroleum Research Fund, administered by the American Chemical Society, and in part by the National Science Foundation (CHE 91-16332 and CHE 94-16611).

DiMaio et al. Supporting Information Available: Tables of atomic coordinates, complete bond distances and angles, and anisotropic thermal parameters for 1 and 2 (15 pages). Ordering information is given on any current masthead page. OM9709998

Electrochemical and Structural Characterization of cis-and trans-[Cp

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